Oxidation process



June 6, 1961 Filed June 13, 1958 ACID NUMBER ACID NUMBER 3 Sheets-Sheet 1 O 25 5O 75 [00' [2S I I go EX.2 5x1 0 TIME IN HOURS FIGURE O 25 5 75 I00 I25 I l I go 0 TIME IN HOURS INVENTORS FGURE a HUGH B. SKEES FRANKLIN E. MANGE ATT NEY June 6, 1961 H. B. SKEES ETAL OXIDATION PROCESS o m 9 B M H x hnl S .v t e e h S w BI o m a E m X E 5 n 8 ul 1 3 l 6 n u J d e l 1. F

TIME IN HOURS FIGURE 3 EX.I5

EX. I2 EX. l4

TIME IN HOURS INVENTORS I F GURE 4 HUGH B. SKEES FRANKLIN E.MANGE BY ATT NEY June 6, 1961 H. B. SKEES ETI'AL 2,987,536

OXIDATION PROCESS Filed June 13, 1958 3 Sheets-Sheet 3 o as so 75 I I I l I =0 EX.I7 EX-IB 1: LL! 0 3 Z EXJQ 0 TIME IN HOURS FIGURE 5 o 25 so I?0 1::

u: LIJ m 2 -so a Z 9 EX.2O u

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EX.25 E 2| X. EX.24 5x27 0 TIME IN HOURS FIGURE 6 INVENTORS HUGH B. SKEES FRANKLIN E. MANGE B fif AT ORNE gree. trated' by reference to those found in the State of Texas. The composition of tank bottom waxes has been approximately determined. In each instance the tank bottom wax ni ter ten 9 v "2,987,536 r OXIDATION PROCESS Hugh B.-Skees, Aflomand FranklinE. Mange, University City, Mo., ,assigno'rs to Petrolite Corporation, Wil-v mmgton, -De l., .-a;corporation of Delaware Filed June 13, 1958, Ser. No. 741,766 16 Claims. (Cl. 260-451) This invention relates to the oxidation of oxidation re sistant hydrocarbons in the presence of. aiperoxide which is relatively heat stableand non-volatile under oxidation conditions. Moreparticularly, this invention relates to the oxidation of said hydrocarbons with an oxygen-containing gas in the presence of an aralkyl-peroxide. In its mostadvantageous aspect, this invention relates to the oxidation of nondistillable hydrocarbons which are normally oxidation resistant, for example, sour microcrystallinewaxes, hydrocarbons obtained from deoiling petrolatum in the preparation of residual microcrystalline wax, etc., by a process which comprises oxidizing said hydrocarbons with an oxygen-containing gas in the presence of a catalyst system comprising 1) an aralkyl peroxide such as dicumyl peroxide, (2) a basic material such as a non-amino base, and (3) a conventional oxidation catalyst, for example the oil-soluble salts of manganese, cobalt, chromium, vanadium, lead, zinc, etc.

A variety of hydrocarbon waxes and comparable compounds principally hydrocarbon in ntaure have been subjected to oxidation by various methods and particularly by the use of air, ozone, or oxygen in the presence of a conventional oxidation catalyst, for example a hydrocarbonsoluble organictsalt, such as manganese or cobalt naphthenate. I

These waxes and oher non-distillable hydrocarbons employed in oxidation may be obtained by various procedures. For instance, they may be obtained in processes involving the production of lubricating oil, such as from various lube oil stocks and petrolatums, or in processes conducted primarily for the recovery of wax; or they may be obtained from sediment in crude oil itself, i.e., com monly referred to as tank bottoms.

The recovery and production of microcrystalline wax is well known and has been described in the literature. See, for example,QU.S. Patent No. 2,443,840, dated June -22, 1948, to Stossel and in an article on Microcrystalline Waxes, Their ManufactUre PrOpertieS and Uses in the Paper Industry" by Bruce H. Clary in Industry and Paper World, February 1, 1956, page 19.

Recovery of tank bottom waxes is conducted principally in the mid-western oil fields, in Kansas, Oklahoma,

Louisiana, and Texas as well as elsewhere to a lesser de- The difference in tank bottom waxes can be illussuch trace in combination with a molecule having 35 to '100' carbon atoms may actually have significance which is somewhat obscure and subtle.

Although the tank bottom waxes are largely paraffinic in nature, one cannot rule out the possibility that a molecule having 35 to' 100 carbon atoms mayor may not have some other structure such as an aryl structure or more likely an alicyclic structure.

, Even in light of what has been said previously, there is noexplanation for a fact that has been recognized for years, .namely, that microcrystalline waxes, even if one limits: oneself to those found in Texas, fall into two Patented June 6, 1961 "Ice classes; one class consists of oxidation susceptible micro crystalline waxes which can be oxidized readily using a conventional catalyst and using a well known conventidnal .Procedures c as h k describ d i9 ee ti e entitled fOxidation of Rarafifins" by I r. Ernest Stossel, which pp r i t eQ andfiasilq tnal. s s f July 21, August 18, andsepternber l, 1945. The other class of microcrystal line waxes appears to be identical in most respects but for some reason these are not oxidation susceptible waxes and for some purposes perhaps they are even more valuable.

Purely for purpose of illustration,immediatelyfollowing and identified as Table I, is a table showing oxidation of the West Texas microcrystalline wax;(non-oxidation susceptible), the oxidation of anEast Texas microcrystalline wax (oxidation susceptible); and the oxidation of an aluminum chloride treated West Texas microcrystalline wax, all three'waxes being oxidized under the same conditions, namely with the, conventional cobalt naphthenate catalyst by the method described by 'Dr. Ernest Stossel above.

Thus, one can select two difierent microcrystalline waxes, both obtained from tank bottoms and both possibly obtained from the same state, for instance, from various Texas oil fields which are characterized by substantially the same physical properties by conventional measurements, but from the standpoint of oxidation susceptibility by means of gaseous oxidation it. is found that-one class is non-susceptible and the other one is susceptible. The non-susceptible type of wax when reacted prior to oxidation with aluminum chloride or other halides, such as hydrochloric acid, or certain Friedel-Craftscatalysts, becomes oxidation susceptible. The above aluminum chloride treatment was accomplished by heating for approximately 7 hours at C. r The amount of. aluminum chloride used was 10%. Such treatment has been described in the patent literature for example, in US. Patent No. 2,471,102. However, the use of aluminum chloride to render these waxes oxidation susceptible is a long, tedious and expensive process.

Another non-distillable, oxidation-resistant hydrocarbon is an oil separated in the deoiling of petrolatum stock used in the preparation of residual microcrystalline wax. This oil is described in the above Bruce Clary article and sheet under Petrolatum which follows time might vary from to 50 or more hours, for example,

employed for the oxidation tends to increase the oxida- 3 tains. an average of 6 naphthenic and 3 aromatic carbon atoms. It contains no materials which will complex with urea, indicating that it is highly branched. It has the following spccificationsz Q 1 "v Flash 7 1 400 F. ravity (API) 26/32 Oolor' dark Vise. 21o (Saybolt? 80/120 Cold test 70/110 3.5-. and W.' 1% mx.

- We have now discovered that non-distillable oxidation. resistant hydrocarbons, such as those described above can bemostadvantageously oxidized without the conventional AlCl pretreatment .by a process which comprises (A) oxidizing said. hydrocarbons with an oxygen-containing gas in the presence of a catalyst system comprising 1) an aralkyl peroxide, such as dicumyl peroxide, (2) a basic material, such as a non-amino base, and .(3') a conventional oxidation catalyst, for example the oil-soluble salts of manganese, cobalt, zinc, iron, chromium, vanadium, lead, etc. In addition, these oxidation resistant hydrocarbons can be oxidized, although not as eifectively as with the above treatment, by the following catalyst systems, (3) a base, most preferably a non-amino base, and the conventional oxidation catalyst (C) an aralkyl peroxide and the conventional catalyst, (D) an aralkyl peroxide and a base and (E) an aralkyl peroxide. In fact, the presence of the aralkyl peroxide, enhances the effectiveness of any particular catalyst system we have tried. However, the most effective results are obtained with (A).

The oxidation process bons. In general, these processes comprise treating the hydrocarbon stock with an oxygene-containing gas such as air, ozone, oxygen, etc., at a temperature above the melting point of hydrocarbon stock, but below its decomposition temperature, such as the range of to 200 "C., for example, to 160 C. but preferably to C. The oxidation is continued for a sufiicient length of time to give the desired acid number which 10't'o 30 hours, but preferably 15 to 20'hours. Of course, 50 it will be' realized that there is an inter-relation of temperature and time for each particular system. Other variations also tend to influence the oxidation. For example, the finest possible division of the oxygen-containing gas 55 tion rate. Increasing the: oxygen pressure also accelerates the rate of oxidation. The rate of air addition can vary widely, such as from 0.1 to 20'rnl./g/min., for example, from 0.5 to 5.0, but preferably from 1.0 to 3. Of course, other factors will influence these rates. For example, with pure oxygen or oxygen enriched air, lower rates can be used- On the other hand, higher rates would be required if the oxidizing gas is not finely dispersed.

Examples of the usual oxidation procedures are described in US. Patent No. 2,249,708, datedI-uly 15, 1941, to Hicks-Bruun; US. Patent No. 2,486,454, dated November l, 1949, to Zellner; US. Patent No. 2,573,422, dated October 30, 1951, to Fish; and US. Patent No. 2,674,613, dated April 6, 1954, to Nelson. Also, the three-part article entitled Oxidation of Paraflins by .Er'nestStossel inThe-Oil and Gas Journal, vol. 44, N o. 11,

ppl309;.No. 15 pp. -51; No. 17, pp. 69-77 (1945) .shouldbe especially noted and also the 121 references in this article.

The oxygenationproduc'ts of the inventioncan vary 7 widely depending on the use for which they are intended. For convenience, the main criteria we employ 'for determining the extent of oxidation are acid numbers. In general, we prefer that the oxidized product have an acid number of at least 10, for example, 10 to 100 or more, but preferably 25 to 70, and a combined oxygen content of at least 2%. However, the optimumam'ountof oxidation can be varied according to theuse" intended.

For example, for use as EBmlLISifiEbIG WQ L KhE- product should have an acid number. of atleas tf 10-f5 but preferably about 20 to 40.

The oxidation can be carried out in a batch or continuous operation. In the case of the continuous operation care should be'taken. that, if possible little,-if any, admixing of the fresh wax stock occurswith the al eady oxidized product. That is the product introducedfand passed through theoxidation apparatus. inja uniform manner. This can be achieved byihe following. provision: (1) Oxidation in several reaction vess.e'ls,,'placedf one aboveanother, or in series; '(2) oxidation in sub-divided reaction vessels, or expediently in pipes;.,( 3 oxidation in a. reaction coil, arranged; in a spiral inwhich the-wax is introduced at the top and the reaction product leaves at the bottom.

The basic material Any basically reacting agent capable of enhancing the oxidation of the diflicultly oxidizable materialv can be employed. In general, the basic material is a non-amino base.

They can include theuse ofv alkali: metal-and. alkaline earth metal hydroxides; oxides, alkoxides, andalso salts ofthese metals with weak, inorganic and organic acids, for. example those derived from group IA and 11A of the periodic table.

As examples of the alkali metal and alkalineearth metal hydroxides, there may be mentioned sodium hydroxide, potassium hydroxide, lithium. hydroxide, calcium hydroxide, barium hydroxide, strontiumhydroxide, and magnmium hydroxide. The alkoxides arerepresented by sodium n-butoxide, and the corresponding potassium, lithium, calcium, strontium-,barium and magnesium alcoholates. Exemplary of the alkali metal. salts-ofweak inorganic acids are sodium tetraborate, tri-sodium phosphate, and potassium carbonate. Examples of alkali metal salts of weak organic acids arethosealkaliimetal salts of acids which formsoaps, such: asthe higher. fatty acids, for example, stearic, oleic, pa1mitic, lauric, linoleic, ricinoleic, the commercially available. mixtures obtained by the hydrolysis or saponification of commercial oils or fats; the resin acids or commercial rosins and their modifications, such as dihydroa biete acid, tetrahydroabietic acid, dehydroabietic acid, hydroxytetrahydroabietic acid, hydrogenated rosin, disproportionatedor dehydrogenated rosin, and polymerized rosin; and thenaphthenic acids.

Basically reacting agents foundto be of. particular value in the process include the alkaline earth metals, calcium, magnesium, strontium and barium and the e ides, hydroxides and carbonates of these metals; the basically reacting oxides, hydroxides, and carbonates of the metals of the iron group'which. metals include iron, cobalt and nickel; the basically reacting: oxides, hydroxides and carbonates of the metals of the right-hand column of group II of the periodic table which are not classifiable as alkaline earth metals, which'metals include beryllium, zinc, cadmium and mercury; and the oxides, hydroxides; carbonates and bicarbonates of the alkali metals sodium, potassium. and lithium.

In employing these basically reacting agents, we may use them in finely divided form,'such as in the form. of a powder, or those which are' water soluble" may be used in the form of a dilute aqueous solution. The powdered compounds may be made into a slurry or'othe'rwise suspended in: the hydrocarbon fraction-being oxidizcdiand the suspension maintained by" means" of'mechanical agitation and/or 'by means of air, or other oxygen-containing agitation during the oxidation process. In a batch operation suflicient of the basically reacting agent may be added at the start of the oxidation or a portion of the required agent may be added and sufiicient additional quantities added during the progress of the oxidation. In a continuous operation, it is 'generally'preferable to mix the total quantity of basically reacting agent with the hydrocarbon feed to the oxidizer.

When employing water-soluble basically reacting agents an aqueous solution of the agent may be injected into the oxidation unit with the feed, with the air or oxidizing gas or at any other convenient point. Thus, a saturated aqueous solution of calcium hydroxide containing an excess of calcium hydroxide may be injected into the oxidation vessel in suflicient quantities. Aqueous solutions of alkali metal carbonates, bicarbonates or hydroxides may be similarly employed.

7 'In usin g the alkaline earth metals themselves, it is convenient to use metal turniiigs or shavings, supporting them on trays or racks the oxidation vessel. As a modification ot the above processes, metals and other agents described which are not appreciably water-soluble may be employed in the form of shavings of granules of any convenient size in a. secondary vessel outside of the oxidation vessel and the neutralization of acids effected by continuously pumping the hydrocarbon being oxidized from the oxidation vessel to the secondary vessel where it is contacted by the basically reacting agent and then returnedto the oxidizer.

, The amount of basic material employed in the catalyst can vary from 0.1 to 3% or higher, for example, 0.2 to 1.5%, but preferably 0.25m 0.75% based on weight of hydrocarbon. Of course, the weight might vary somewhat according to the molecular weight of the base relative to its effective basicity.

The conventional oxidation catalyst The term conventional oxidation catalyst refers to those metallic. compounds heretofore conventionally employedby the art in the oxidation of wax type hydrocarbons, for example, compounds of manganese, cobalt, lead, iron, .nickel, copper, vanadium, chromium, mercury, zinc, etcf Since greater activity is achieved by using a soluble compound these are preferred; Metal salts of organic acids are particularly useful in this invention. Exemplary of such salts are manganese-butyl phthalate, manganese linoleate,manganesse'naphthenate, a mixture of manganese and .lead acetates, cobalt linoleate, cobalt naphthenate, mixed leadcobalt naphthenate, the metal resinates snchas manganese, cobalt, 'zinc, etc. resinates derived from any rosin acid such as abietic, pirnaric, dehydroabietic, dihydroabietic, tetrahydroabietic acid, cobalt acetate, cobalt oleate,.cobalt stearate, and corresponding organic acid salts of the other metals can also be employed. Other examples of conventional oxidation catalysts can be found in the patents describing the oxidation of hydrocarbons disclosed in the section of this patent relating to the oxidation process. In general, these catalysts are heavy metal compounds.

The conventional oxidation catalyst can vary from .1.

to 3% or higher, for example, 0.2 to l.0%, b'ut prefen ably 0.3 to 0.7%, based on weight of hydrocarbon. These figures are based on cobalt naphthenate containing 6% cobalt, the preferred catalyst. For other catalysts, these figures will vary somewhat according to the molecular weight of the catalyst relative to the percent of metal present therein.

The peroxide Although many peroxides aid somewhat in the present. foxidation system, their effect is generally dissipated before a suitable acid number is obtained. For example, when. dib'enzoyl peroxide is employed, its presence is effective in" employed, one obtains'the superior results of this inven-- tion; These peroxides are represented by'the structural formula where Ar is an aryl group, for example, phenyl, naphthyl, anthryl, phenanthyl, etc; The aryl group may contain alkyl substituents asin'the case of isopropylphenyl, butylphenyl, isobutylphenyl,,.'ebutylphenyl, pentamethyl, ethylphenyl, dimethylpheriyl, methylethylphenyl, etc; and the corresponding alkyl derivatives of the other aryl groups mentioned above. .Thus,,the term aryl includes, alkaryl groups; The aryl group mayalso contain othergroups that do 'not interfere with the usual effect of the peroxide on the instant catalyst system. R R R and R which may? be the,,sarrie -or-Idifierent, are hydrogens or alkyl groups of le'ss'tli'an 4 carbons. R is hydrogeman alkyl of less than 4 carbons, or'A-r, which has the same meaning as Ar of the, present formula. Where R is Ar it need not bethe, sameas the other Ar group. i j In other Words these peroxides contain'one or-two aryl groups. They maybe symmetrical or unsymmetrical and mixtures of them may be employed.

In general, the peroxides of this invention are characterized by containing at least 10 carbon atoms and usually not more than about 40 carbon atoms. Specific peroxides preferred in the invention are methyl (a,a-dimethylbenzyl) peroxide, tertiary butyl (a,a-dimethylbenzyl) peroxide, methyl (a,u-dimethyl-p-isopropylbenzyl) peroxide, and methyl (a-a-dimethyl-p-methylbenzyl) peroxide, bis (a,a-dimethylbenzyl) peroxide, bis (a,a-dimethyl p methylbenzyl) peroxide, and his (a,a-dimethyl-p-isopropyl-benzyl) peroxide. 'Ihe peroxide most advantageously employed is dicumyl peroxide [bis(a,a-dimethyl benzyl) peroxide].

The class of di(aralkyl) peroxides of this invention include the following symmetrical or bis(a.ralkyl) peroxidesz dibenzyl peroxide, bis (at-methylbenzyl) peroxide, bis(a-ethy1benzyl) peroxide, bis(a-propylbenzyl) peroxide,- bis(oa-isopropylbenzyl) peroxide, bis(u,a-dimefihyl'- benzyl) peroxide, bis(a-methyl-a-ethylbenzyl) peroxide, bis( 0:,a-(li6thYlbBI1ZYl) peroxide, bis(u,a-dipropylbenzyl) peroxide, bis(e,a diisopropylbenzyl) peroxide, bis (11,11.- diisopropylnaphthylmethyl) peroxide, bis(d,a-dimethylnaphthylmethyl) peroxide, bis(a,a-dimethyl p methyl benzyl) peroxide, bis(u-methyl-a-ethyl-p-methylbenzyl) peroxide, bis(a,a-diethyl-p-methylbenzyl) peroxide, bis- (a,a-diisopropyl-p-methylbenzyl) peroxide, biS(a,a di methyl-p-ethylbenzyl) peroxide, bis(a-methyl-u-ethyl-pethylbenzyl) peroxide, bis(a,a-diethyl p ethylbenzyl) peroxide, bis(a,a-diisopropyl p ethylbenzyl) peroxide, biS(a,oz dimethyl p isopropylbenzyl) peroxide, biS(a methyl oz ethyl-p-isopropylbenzyl)peroxide, biS(a,a-diethyl-p-isopropylbenzyl) peroxide, bis (a,a-diisopropyl-pisopropyl-benzyl) peroxide, bis(a,u-dimethyl-p t butylbenzyl) peroxide, bis(a-methyl-a-ethyl-p-t butylbenzyl) peroxide, bis(a,e-diethyl-pt-butylbenzyl) peroxide, bis (ace-diisopropyl-pet-butylbenzyl) peroxide, biS(oc,cz-di methyl p pentamethylethylbenzyl) peroxide, bis (amethyl a ethyl-p-pentamethylethylbenzyl) peroxide, bis (a,a-diethyl-p-pentamethylethylbenzyl) peroxide and bis (a,u-diisopropyl-p-pentamethylethylbenzyl) peroxide.

Unsymmetrical diaryl peroxides of this invention containing two aryl groups include the following compounds. benzyl(a methylbenzyl) peroxide, benzyl(a-methyl p methylbenzyl) peroxide, benzyl(a methyl p-isopropylbenzyl) peroxide, benzyl(a,e-dimethylbenzyl) peroxide the catalyst system for'only a short period of time after y -(m yl p-methylbenzyl) peroxide, benzyl 7 (mtdimethylsp isopropyl 1 l')i peroxide, a-methyl benzylfme-dimethylbenzyl peroxide, m-methylbenzylw, adiiriethylspmethylben'zyl peroxide;v u-methylbenzylw, uedimethyl -p-methylbenzyl) peroxide", a-methylbenzyKa, cediemthylepi-isopropylbenzyl') peroxide, -isopropy1benzyl (a,a-d.iisopropylbenzyl) peroxide, a,a-dimethylbenzy1(a, a-dimethyl-p-methylbenzyl) peroxide, a,a-diisopropylbenzyl-(a,adiisopropyl-p-nrethylbenzyl) peroxide, and a,u-diisopropylbenzyl (a,aAiisopropyl-p-isopropylbenzyl) peroxide.

' The peroxides of the invention are nonvoltatile peroxides, haying a vapor pressure sufliciently low at oxidation temperatures to prevent substantial loss of the peroxide duringoxidation. The: nonvolatileperoxides of the inventiona'ref thus distinguished from volatile peroxides such as di'(ffertiary"butyl) peroxide. In general, the peroxides of the invention hfve boiling points greater than about l50 I peroxides of the invention decompose at a moderate rate under oxidation conditionsto' form free radicals. Thusgjfor' example, methyl '(o;,a-dimethylbenzyl') peroxide decomposes to form a methoxy free radical and an am-dimethylbenzyloxy freeradical. The decomposition of the peroxides is almost entirelydependent' upon temperature'. f I

"The peroxides of the invention can be prepared by methods known to the art. A particularly convenient method. involves condensation ofthe corresponding alcohols of the general formula 1 and hydroperoxides having the general formula wherein A R R3, R R and R are the same as in the general formula given hereinabove. The amount of alcohol' utilizedshould be at least the theoretical calculated amount to combine with all of the hydroperoxide and preferably slightly in excess of this amount. The condensation of the hydroperoxide with the alcohol is carried out in: the presence of a catalytic amount up to about 0.5% of an acid-acting condensation catalyst based on the weight of the alcohol, and the temperature used is preferably between SO -120 C. p-toluene sulfonic acid can be utilized-as: the-ac d-a fi on ns i n y ts droperoxides and alcohols mentioned; above may beprepared in accordance with processes well known'tother The peroxides ofi'the invention in which R R and R are all. hydrogen can be produced conveniently bywa tacting aralkylhydroperoxides dirnethylisulfate invert; aqueous alkaline medium. For example,.methyl (a, -dia; methylbenzyl) peroxide ,can be; produced by dispersing: cumene hydroperoxi'de with rapid stirring in an aqueous solution of sodium hydroxide while. gradually adding a stoichiometric amount of dimethylsulfateand maintaim ing the temperature at about ZS-30 Cr After all the d imethyl sulfate is added and the reactionis completeythe methyl (ma-dimethylbenzyl) peroxide'canbe takenupin petroleum ether and'washed freeof cumenehydroperoxide with 10% aqueous sodium hydroxide, 1 'Ihed'esired peroxide can then be recovered :in ajpurityof v about-%, by distilling off petroleum ether. p I p j The amount of peroxide utilized-in the catalyst system of'our invention can vary within wide limits, depending upon the particular hydrocarbonoxidi-zei and its oxida; tion resistance. 7 Of course, highconcentrations can be employed if desired,- but the economies of the process require the'most efiicient use of the peroxide-.1 Thus, a 0on centration of 0:2 to 4% or-higher of-the peroxide based on weight of the hydrocarbons, forexample, 0.3 (02.0%. but preferably 0.5 to 1.0% can be employed.

The following examples are presented to illustrate our invention. The percentages'of catalyst employed are by weight percentages based on the weight of the hydrocarq bon stock.

In general, the hydrocarbon stock is oxidized at C. by blowing air at the rate of 2-3 mL/gJmin. through a sintered glass disperser into the molten hydrocarbon stock under the conditions indicated in the following table. The following non-oxidation, susceptible hydrocarbon stocks are oxidized: (l Ultraflex Amber-a plastic microcrystalline wax derived from petrolatum stock by a centrifuge process andthen bleached to a color of ZNPA by percolation through activated clay. It has a melting point of 145 F. (ASTM test method D127-30) and a penetration of 25-30 at 77 F. (ASIM test method D5-25); (2) Bleached West Texas Microcrystalline Wax-a hard microcrystalline wax obtained from tank bottoms from'West Texas crude oil, which is a sour crude. Bleached West Texas crude is derived from this sourcrude and bleached by percolation through activated clay to a color of about 1.5 N'PA. It still has the characteristic sour crude odor. It has a melting point of 1 90 -200 F. and a penetration (Pen 100/5 71 F.) of 4-5 at 77 F.; and (3) Black V-Oil, which has. been described above. Bleached V-Oil has substantially the same properties: ex.- cept that it is lighter in color (.1 to 2- NBA). Itis bleached with clay. The black. V-Oil. is more oxidation resistant than the bleached V-Oil.

TABLE II ULTBAFLEX AMBER MIOROORYSTALLINE WAX Acid Number Percent Percent Conven i n l Ex. Peroxide Peroxide Base Base Oxidation Catalyst 5 10 20 30 40 .60 80 hrs. hrs. hrs. hrs hrs hrs. hrs

1 None N n 2.--- MgO. 1.0 do 0 0.3 0.2 0.7 0.3 0.2 1.8 3-. Nona rln 1.2 2.4 3.5 5.0 7.6 16.0 36.8 4 Mg0 1.0 ----do 0.8 1.9 v6.8 20.0 53.0 68.0 5-. d0 MgO--..- 1.0 do 1.8 5;0 15.3-17.8 46.5 6. Dibenzoyl-- Mg0 1.0 ---do; 4.3 6.3 8.8 15.0 23.5 7. Dicumyl Peroxide MgO.-. 0.25 ---do'. 0.9 2,5 9.4 17.6 27.5 Mg0 0.5 .06 1.7 7.0 -14;0, 22.5

MgO 0.1 do 0.2 1.2. 5.0 9.5 13.8 16.21.

1 Substantially no oxidation during 80 hours.

7 .TABLE 111 WEST 'rnxss mono-orars'rxnnmn wxxnLmcnnn Percent T Percent Percent Conventional Oxida- Oonven- 20 30 .40 Ex. Peroxide Peroxide Base Base tion Catalyst .tio hrs; hrs. hrs.

I Oxidation I Catalyst DicumylPeroxide. 2.0 MgO 1.0 Non 1.2 2.3 6.6 15.6 20.3 DlbenzoyL .ao MgO 1.0 do H 6.0 5.4 4.8 e (me N CobaltNaphthenate 0.5 50.4 10.6. 1.2, 2.1 2.5,

rln MgO 1.0 do 0.5 0.2 0.6 2.0 20.5 56.0 Diomnyl Per0xide- 1.0 N n n '0.5 0.8 -1.4' 2.4 2.6 -*2.7

dn 1.0 MgO 1.0 None 0.2 0.3 1.4 3.1 4.6 fin 1,0 Mg0- 1.0 Cobalt Naphthenaten 0.5. 3.0 14.1 37.5 57.7 81.0 do 1.0 MgO 1.0 55 t 3 j 0.5 0.1 as 39.5 50.2 75.5 do; 1.0 OH= ONa. 0.5 do. .;----t-;' 0.5:, 2-5, 1 45 40.0 56.5 6

N n N s mminp m mm TAB EIV 1 1 1,:

" BLEAOHED V-OIL Pe cent Ex. Percent Percent Cdbalt 5 10 Z) 50 60 Dleumyl Base Naph hrs. hrs. hrs. hrs. hrs. hrs. hrs.

thenate 1 Substantially no oxidation during 60 hours. The data obtained in the above table is presented in the We claim: drawing in which FIGURE 1 through FIGURE 6 are 0 1. A process of oxidizing normally nondistillable oxigraphs wherein acid number is plotted as a function of time in hours. The number identifying each curve refers to the examples in the above table.

From the above examples and graphs, it is evident that:

(1) The hydrocarbon stocks are substantially non-oxidation susceptible when oxidized (a) without any catalyst, (b) with only the base as a catalyst, (c) with only the conventional oxidation catalyst.

(2) The hydrocarbon stocks are more readily oxidized by a catalyst system containing both the conventional oxidation catalyst and the base than by either one alone.

(3) The hydrocarbon stocks are more readily oxidized with or without any other catalyst, provided the peroxides of this invention are employed. In other words, these peroxides enhance the efiect of any particular oxidation system.

(4) The hydrocarbon stocks are most readily oxidized with a catalyst system containing the peroxides of this invention, a base, and the conventional oxidation catalyst.

The products of this invention can be employed in many applications, for examplethe oxidized microcrystalline wax can be employed in wax emulsions, polishes, which can be spread on surfaces such as linoleum, wood floors, furniture, automobiles, etc., to give a finish which dries to a high gloss. These oxidized hydrocarbons also find use as additives for lubricating greases or as additive in various hydrocarbon coating for metals which, in addition to enhancing the physical properties, they also have a tendency to inhibit corrosion. In addition, these oxidized hydrocarbons can be employed as the acid moiety of salts of various amines, for example, the Duomeens, RNH(CH,) NH=, where R is a hydrocarbon radical, for use as corrosion inhibitors, in oil wells, slushing oils, etc.

dation resistant petroleum hydrocarbons which comprises oxidizing said hydrocarbons with an oxygen containing gas at a temperature above their melting point but below their decomposition temperature in the presence of at least 0.2% of an aralkyl peroxide having at least 10 carbon atoms and boiling above C. which is relatively heat stable and non-volatile under the oxidizing conditions.

2. The process of claim 1 where the peroxide is dicumyl peroxide.

3. A process of oxidizing normally non-distillable oxidation resistant petroleum hydrocarbons which comprises oxidizing said hydrocarbons at a temperature above their melting point but below their decomposition temperature with an oxygen containing gas in the presence of at least 0.1% of a basic material and at least 0.2% of an aralky-l peroxide having at least 10 carbon atoms and boiling above 150 C. which is relatively heat stable and nonvolatile under the oxidizing conditions.

4. The process of claim 3 where the basic material is a non-amino base.

5. The process of claim 4 where the peroxide is dicumyl peroxide.

6. A process of oxidizing normally non-distillable petroleum hydrocarbons which are normally oxidation resistant which comprises oxidizing said hydrocarbons at a temperature above their melting point but below their decomposition temperature with an oxygen-containing gas in the presence of (1) at least 0.2% of an aralkyl peroxide having at least 10 carbon atoms and boiling above 150 C. which is relatively heat stable and non-volatile under the oxidizing conditions (2) at least 0.1% of a basic material and (3) at least 0.006% based on metal content of an oxidation catalyst.

7. The process of claim 6 where the basic material is a non-amino base.

seams 111: 8. The process of claim 7 here the peroxide is dicumyl peroxide.

9 The process of oxidizing normaliymon-distillable oxidation resistant petroleum hydrocarbons-which comprises oxidizing said hydrocarbons with am oxygen-con- "I the group consisting of a group IA base and a group tajnin gasgat ternperan L 'eabove their meltingpoint lint below their decomposition temperature 'with an oxygen containing gas in the presence of (I) at least 0.2%

dicumyl peroxiciti) ail east 01% diaries-ammo Ease selected fro'm the g'r'ou 'a consisting of alkali metal and alkaline earth salts and (3') at least .0U6%,f based on metal content of an oxidation-' catalyst containing a heavy metal.

1 mime process of'clain i 9lwhere'in the oxidation;

catalyst is selected the-group consistingaof cobalt and manganese compo'u'ndsj -r T1. The process of claim 9 \T/lieretfieoxida'tion resistant hydrocarbons are a microcrystalh'ne wax. V

12. The process of claim 9 where the oxidation resistant hydrocarbons are an oil extracted from petrolatum stock.

7 base and an: oil soluble heavy metal compound.

14.- The process of claim 13 where the process. is car, ried out in the presence of MgO and cobalt naphthenate. 15. The process of claim 12 where the process is carried out at '-l'60 C'. in the presence of a member selected from the group consisting of a group IA base and a group IIA base and an oil soluble heavy metal compound. v 7 i I 16."The process at claim 15, whereithe process is car-' ried out in the presence of MgO and cobalt naphthenatel' Referenc'esCited in the file ofthis patent UNITED STATES PATENTS Garret al. ;Iune7;-1-93-8 Merl'ey et' al. Hint-J20; 1953 Margaret al Mar. 15, 1955 I Armafile et al. May 28, 1957 13. The process of claim 11 where the process iscarried W V 7 am. it 

6. A PROCESS OF OXIDIZING NORMALLY NON-DISTILLABLE PETROLEUM HYDROCARBONS WHICH ARE NORMALLY OXIDATION RESISTANT WHICH COMPRISES OXIDIZING SAID HYDROCARBONS AT A TEMPERATURE ABOVE THEIR MELTING POINT BUT BELOW THEIR DECOMPOSITION TEMPERATURE WITH AN OXYGEN-CONTAINING GAS IN THE PRESENCE OF (1) AT LEAST 0.2% OF AN ARALKYL PEROXIDE HAVING AT LEAST 10 CARBON ATOMS AND BOILING ABOVE 150*C. WHICH IS RELATIVELY HEAT STABLE AND NON-VOLATILE UNDER THE OXIDIZING CONDITIONS (2) AT LEAST 0.1% OF A BASIC MATERIAL AND (3) AT LEAST 0.006% BASED ON METAL CONTENT OF AN OXIDATION CATALYST. 